Process of manufacturing nitrogen compounds from atmospheric nitrogen.



Patenmwse t. 30, I962 c. s. BRADLEY & u. n. LOVEJOY'.

PROCESS OF MANUFACTURING NITROGEN COMPGUNDS FROiflATM9SPflERIG NITROGEN.

. (Nd Model.)

(Applica ion filed Mar. 9, 1900.)

3 Shasta-Sheet I.

No. 709,357. Patented Sepi. 30, 1902..

' c. s. BRADLEY & n. R. LOVEJOY. PROCESS OF MQNUFACTUBING NIT QUEENCUMPQUNDS FROM ATMOSPHERIC MTRUGEN.

7 (Application filed Mar. 9, 1900.) v 4N0 Model.) 3 Sheets-Sheet 3. V

ilr'rwmi STATES ATENT FMQEQ CHARLES S. ERADLE Y AND DIMMIT" ROSSLOVEJOY, OF NEW YORK, 51. Y

ASSEGNORS, BY M ESNE ASSIGNMENTS, TO ATMOSPHERIC PRODUCTS COM- PANY, OFNIAGARA FALLS, NIHVYORK, A CORPORATION OF NEWV YORK.

PliGCESSQF MANUFACTURING NITROGEN ODMPOUNDS FROM ATMOSPHERIC NITfiGGfii.

SPEQKFVLQIEEOE forming part of Letters Patent No. 709,867, datedSeptember 36, 1902.

Application filed Til arch 9,1900. fiariol-Noofliilfiil. (No specimens.)I

1" wZZ w/z om it Hwy 80J2/C677b:

Be it known that we, CHARLES S. BRADLEY and DIMMITT Ross LOVEJOY,'oiiizens of rho Unitefi States, residing: at New York, in the 5oouzityaoil fair-rho of New York, have invented cos-Lain new and usefulimprovements in Processes -for tho Mmiiifaoture Nitrogen .Coinpoumisfrom Atmospheric Nitrogen, of

which the following is a speciiioiiiion.

This inveiiiioh reiz xtes 50 H, proooss for tho manufacture of ziitrogrncompounds from an mospherio nitrogen; and its ohjeoa to docroaso theexpendiwre of energy and mate-- rial in the production of such oomgoumis. 5 The presoiit process is on rho eomlir nation of iiiirogen andoxygzon by moons of tho oleo rio ourrrnt missing ihr yzh a mixture of :5oh Vie hora found lhritiho amount of nitrogen oompoiiii produced isdependent to a. large axiom on Silo relation between amour]; electricenergy op plied and. the amount, of mirrors e1-1- posed lo the action ofsuch 9116x135, zimi our invoigrioii directed in part to rho proportion-5 ihg' of Lilo qllllli'lllilfii of electric em-rgy and of or lllliedgases 20 give ouch iil f illilifi Jfii3i6ll3lpl Another im iortzuirfoaiiirooi our process rehiies, to aim maintenanoool theE?l2(l!i00llirem when i; ii; passing through Lire mixed arisen in. ahaform aiizipteii to give the highosr yield of niilrous prod um. for-rugiven axpon'diburs of energy. It is known that. tho siiont liaohargo isnot oopoblo of producing niLrifi oaiohio any sriiistuiitizil exfieoiz.W6 ham found inai; the OFCli'iHLTY disruptive discharge; or spark is ofcomparatively little ca,-

' s respeot and that foralorgeand oi? nitrous product the useimperative; but we have also than efiioisncy of on are in the profound Wdilation of nitrous product; is dapondem on its form orqua-lity and thatthe most efficient are is thai; which has 25, minimum volume of 5current compatible Willi its exisrenooas a true ore-than is to say, thethinner ilie are the greater the efficiency up no Lhe poinr, Where whoare gets so thin than it brooks or cannot;

be maintained.

0 an arc probably due to the comparatively The high efiioioncy of such.

large surf-(me exposed to the airoompared to the amount of energyinvolved, thereby insuring the maximum synthetic efiioclizuid thisminimum of disaxsoriasihg 959m]. A thin: arcoi' this nature, however,necessarily rep resents a qiiire limiied amount; of currentsay about;(ms to 2-2:: iillvlmflifllivlltl of me. ampero rimi in order to obtain areea'sooabiy. hirge produciion from a single energizing source is isiherefore nrurs s-(iry 11o suhdiviiis the current. from W2 5i: source.in such division of rho ourrem it is necessary or; oocoum of lhs; highwillow To ii -range she circuits lil pm-alloi, and when thisllcfllfillfi the are HMM'ES it tends to aci as a, short circuit f allihe other sire-circuits mid provenia smiling of any othei aro. To -ii/ercoziio iii we provide transformers or indoor-2.210% so arrangsdihatrho sudden divarsiozi of energy to any one eirouit. is prevemoil, earl(l We also provide moans wl orohyoaioii individual, is inierriipteiiShortly z-ifnor ii slowly-mat i2, iho arcs are iiiiormittemlyimrrrnptod-so that; opggormniti-es each zirooirwi o hr hoko ourro .i; moheziiig in rapid suooession. iuasmiioli m; cor

ezwrziliy supplied from a soiirco L a Y iil fl'ei. i s? more our-rem inlfiSflUiL-KHQ to doors-moo 0i reiiis'sanoo, in is apparent. that thomomem are has sijortetl ib will Land to grow in rolumo. Thus assuming:that sufileiona voltage is snppiieii to jump "ehe space isrmveonterminals form a thin are resisianoa o; the air will on rimming of theare iiiimedimely decrease and rho volume of rho are will immediatelytend to increase. As abovepoimecl oub it is desirable to maintain thearc (1.11 the minimum thicknoso orroliiiiio. this onri We arrangeio'caose each are 1mm -a to be drawn out or eloogaied, so as-to maintain the resistance and produce an arc of minimum thickness, whichelongates m a certain extent; and [hell breaks, the rapid repetition ofthis process proilhcing the in- Lermittenoo of the arcs above'referredto.

Our invention also comprises certain improvements in the methods ofcolleciin'g Llio all (in: sttt-itza vpnriitimhein -partictiim'lg'adaptcd to alternating; \"fllll'iflhli. Fig. 53 shows i n ilctz-til 2isingle unit cf the installation lllUS' z'riiierl in Figv i. Figs. ii andi show a mothlicabion of the ip mrnttts adapted for directctirrent. Fig.5 shows the complete installalaiion of devices cmtstrttctoti accordingto Figs. Z3 and l Referring: to Fig. l, A plurality of receivcrs areshown at 1, iahcsc receivers being cf glass or other suitable material.inlet and Outlet. tllltlS or passages '2 3, respectively, at t mebotiotrt illltl at. one side (if the rcspcciivc rcccivers prcridc fcrthe passage of air through thz same, the passages 3 leading to thecure:- :tir or to H. source ui' nil and the passages 3 nciitgccmmectetli.( j iiclivery-pipes l, leading to thc (folluciittg apparatus. 'lwcterminals 5 6 51M! scalett through mid inn) each receiver, so as to bein prc inity at, some paint (indicated 14b T) and diverging, trmn thispoint in any dc- Hll'Qil :lirccltiun. in this case the divergence is ntwartiiy, with the result that when an arc is struck bctrvvccnthciawoterminalsit, will travel upwardly tinder the influence of thedraft. caused lay its cvcn heat or by reason of the (tlr-cnrrctii ilrlizcred through the aibr-ceptw al or for an miter reason, and willilicrcby lzcccmu rapid y eloiigztietl or drawn: out, thus ihc sniitlcndecreased lQSlSl-ENICB t time of current that; would tmhcrwise mi), andfinally the arc will snap or it the (ends of the llllllllzkli-l beforeLite llill'lll'ifi into ii spark, this c perziiinn t 5: placerepeatedly, ii, beiii understood that, the voltage delivered to sheterminals just sut'licieut to insure its breaking across Llic nzirrcwcsrpat-00f tlzcair-gar; between the 'il!lliiilS. I; 1 important m brcal:the arcs in such manner as to prevent fcrtnniion of pm-l as the maincft'cct of the Miter is to ozone, while for nitrification arcs are inureciiicicnt. The several arc-suprflying circuits 3 S are supplied from thesecondary coils 9 of transformers whose primaries 10 are ccimccicil inparallel i-c theenergizing-circuit 1], which may he energized i'rnm anysnii l0 SUtlI'CL" "such as i hc alternating-current :n'zilcr 12.1. 'llicl'epeilifill iiitierrtt iticn 01 rule at; Slhll'ii intervals by the:itttmnitLic opera on of the ilcviceszilmrv (ltf'iifl'lhfld minis L0cnzihlc the distribution of lhe nstcr itwecai the ia'LVGIiLl receiversor nilrii'yiirsr tl 'ices l twin order to insnm Filttll ttnitm'tn iis-'Ll'llvililtkll iltc SCPHliilJlOl) ui' t-hn lIlLllYltllltil zircciruuiirz, :w; by their connection it) scpiir trzmsforntcr-ciruuitis, isessential, elm 7 l wise, t-ltura would be it tendency to (Ullijill'nticn (if all the clcc'tric ciwrg in one or :i luv: oi tii. mes.

may use any suitable means; lillt in tn' 'lm i0 zt-voitl ilie use ofabscrhing iilPlllEL Fil tlt its :tlkaline solutions and to cbiziin tlK-prmlmt in the most concentrated and vitlnzihlc tm'tn Wc ii-Mr i0cpcrattc by :ihsnr iinn in f'lilifllill. HCltl and subsequent rctnuvzilfrntn the ah- 7;

i 0161 by llnulllil or to cptam'tc hy' lr (ions-(Erich of nitruus;products int-i ii .iquicl form by exposure of the stir conmiir lug srrchproducts to asnitzi'nlc degree of call]. I In eitiicrcase the nitrousproducis are :lcliverctl sttch-[. 9., as anhydrous ()Xitls cf Elltrogcn.In ccllccting the products cyihc int-c of sulfuric acid the apparatusrcprcsent'ctl in Fig. i may hi) used, the same comprising a. tubularcmviuibcr ic-Wer 1%, through. which the gases from the nitri yingapparatus are drawn in {ill upward direction, while sulfuric acid is-Jsupplied at the top cf the tubular coir dttit and trickles over the 0wructiingc iiizl'W rial l5 placed therein, absorbing in lLE- :imrnwardpassage substantially all of the niLrcns product cotzmi'ncil. in Elnatii anti iinitll 1m ing inLc 2t rcccptaclc 1%, which is iacpi WPUZ). byBill able heating means 17, 170 as in llc'ili the sulfuric acid sttfii'1 It; @itttsc ei-rpiil- 5 sion of the nitrous prod *ipiwr, SUCH r21,-por passing oil throng )l'lll iii in cooler 15:

to the rcccpizaclc 20. pump 21 draws the suli'nriczmiil llllOligll a.turn-misc 5 ing through conic! lsltn air 1 vardly in the rnbnlzar ccrmll dra the niirificti air llirohs L a mir v u uni-rent h sti l";receiver prci'ci c 1) 10, cmbecticd i 11 lllslllftlil with its secondaryt min wire the ierininzins .28 vice, ilic construction of :ibcre rilevcrihcii. The on 1 of such niirifying ilc'v the fcrih of a nozzlc,slippci into the znc'tith l. 'lfhe primary terminals Iii former arezitiz-igted in contact; with c strips 32 on the shelf 31,0!1 which. blliin placed so Aim, he act 0E putting Lhc transfurmei i place UlUl'Vtlsthe electric ccn 'n tncrcof anti puts it in w th Lion wiiu L. livery/ripe 4-.

The c cciritzal 53 cm 01 subdivision above described if; cspcc .lly a rplliiildl in connection will: ztlternmtnq cm rent. in vicar cf illeerily/(rise involved in the (illill cf the gt'QE-IL number of smalltrzmnmrimars required in such item 'vw,

iewiiiz. the llftl'iii .-.i-. .r=.

ti to prn lti (l of the at; Or

ITO

diatribnliun or ble either vl'ci ual arc-circuits to be effected by themore mterpoeiision in each such circuit of an induoiauce of alightcapacity and correspondingly siiglifi cosi, such a system beingapplicain eoojonctioii with o higzirtezmion direct (current, or WlLli onellernating current of ordinary frequency Referring now to Figs. 3 and4, the receiver llin this case is common to a largre number of arodevelopio z devices or terminals 5 6. Said receiver ooneisi's of iicylinder, preferably of refractory insulating: material, closed all topand bottom by plates or ends 33 of similar material, in which are foundthe inlet and outlet aperiiu res 2 3, The terminals 5 are seiiimoiliecylindricel well of recepiaclel and project slightly into saidreceptacle. On a spindle snoimiecl in bearings 35 andilriveii by motor36, are carried a, plurality of movable termina s 5, preferably arrangedradially on disks 3'? on said spindle, each disk carryaeeriee ofiermihels adapter 1 c operate will: all of the fixed terminals 5 Lhoirploiie of oi-aiioii, The I62! conneote ioduciriai of e circuit-11, com,I this ease a higlviensioo direct-ow agor, whose other side isronnecte-v'. step of ihe spindle 54. ilie spindle is limited by themotor eirucir, interrupted in rapid succession he fixed and moving sermieach mm in animal coming cloeo enough to the fixed i nels in the someseries is) on strikezierossemi then by w, 5 drawing the are rapidly om.By proriziiiw o enifioient no in be? of the movable Iermio-eis 6 amrotating theshaft m; e eiifii lent spceii e periodi of interruption ofahe arse may be ohmineu e say, live hundred to one thousand per seeoml.With such periodicity it is oovious abet; the inductance region-ell iiithe SEV: oral hreoeh circuits in order to effect suiiicieiiielectricalseparation of the circuits, including the dieeher e devices to prevencihe short-cirouliiiog effect above referred to, is exnremely email, andiho cost of the iolioeszmce devices will be proportionately light. infait'i, the in-- duet-ion devices may be of each small inductive effectthat; an alternating current of or dinery frequency may traverse eamewiishoufi any substantial loss, and the energizing circoil; 11 maytherefore be high-tension lowfreqiiency eltereazingcurrem euppiicdeither (iireei, or by siep-up transformers from a suit able alierhetosxIn order to i'ecili'tale re moval, inspection, em; repair of theinductonce devices,we may arrange them on shelves 39 around llie easingof receiver 1 and provide on he body or wee of each imiuctzwoe i. agene:

device terminals 40 41, adapted to eonlaci,.

respectivelyg'willi iheouier ends of the terminels 5 in the receptacle 1and with conemotions 42 on the seili shelves, said eontaci ringebeingconnected ie the chemo-wire 11,

as shown, so that the act of putting themcondensing ably, two coolers 4849, through which the ductance device in place completes its circuit.This construction does away wish the elrilonrate wiring that wouldotherwise be required.

in Fig. 5 is shown a complete insiolieiion comprising devices of theType represented in Figs. 3 and i, inclosed in a room or cha nber 45,supplied with fresh air at the top by means of conduit orilistrihnring-chamber 46 and the air being drawn out at the bottom ofthe receivers l by conduit or main 4, which may im-lmie a trap 47 forarresting, collectlog, and delivering any nitric acid t-hatmay beformed. The-collecting means for the nitrous produci here shown is basedon the principle and comprises, preferplpe 50 from the main l or fromthe trap 47 pal-lees successively. in the first, of these coolers theair is cooled suliiicientlg;-say to about ceniigrade--to condensesubstan- Lieily all of he nitrogen tei soxid (N 0,) which collects in areceiver 51, and ihe remaining {IRS ihen passing aha-0113i: the cooler49 for their cooled sui'ficiently (to 30 cenizigrade or oi-J) iocondense all ilie nitrogen irioxili which is colleeiel'l in receiver thereceiver .52 iiio unaltered. air die- ""ed through pipe inasmuch as this..crged air is extremely cold, we prefer to ii 1%, through regeneratingdevices Lo utilize to undergo the nitrification process *eliminerycooling, so oe to deposit i oiewro iherefroiii, and the apparaiiieadapted to carry oui these several fonct we, represeme an engine, 56 acompress lo l 57 expa ieioireogioe cylinder, all iiv' ievicee beingmechanicallycoeneco ed to m iiioiliy interchange power. The air ie tokenfrom the iil'fi'lOSEl'li'SfE 2,3 58, compressei Au. cylinder 56, ihenihroogh 11 pipe 5e, oooleri by water-cooler and we moisture iscoileceeliand removed in Theair thee peeees by giipe ilzrrogh cooler 63, where mee moistureis trapped O l at 65, mid M192} iorougii the expeneioirengioe57, which further cools ii. i i lolly, the colddry air posses to thecoolers i-Q 48, suecessively, serving as the refrigerating medium forthe air coming from the nizrifying-ehemhers. Theair passes from ihecooler through pipe 65 to con- Liuli 46, which delivers it to theoitrifying devices. This air being extremely dry, the formotion ofnitric acid is reduced to a minimum,

which' is of advantage when the nitrous oxid and uilrogeo tetroxid tocolleoieii such. The further adveotege Represented that corrosion of themetallic of ihe nitri fying epperelzos is reduced toe minimum and byforming parbse-fer e oomle, iiie terminals 5 6-of iron ehey reisubstmztially permanent. From izheiui iuyiiigmhmm berths gas passes asabove described book through the coolers i9, deooeiiing cueoeeeively itsnitro tetroxid, on its nitrous; oxid in the respeci-ive receivers 1passing from the loiater receiver ihrouglz cool- H old. We prefer toeiiojeei no reiziti gm) 1m @ieciriu current, in Lim form of an im:(:EKUH of miwiznum volume, elongating: wi l {H'C and.

The gn oeess of piqtlucing uoii'ipoimds of niircigei'i mid oxygen,consisting in 'removing from .iimoszpiioric air substanaia'ilyaii-r'noisi-m'e 0c ntnin= 1 Ii'lGiPin, the!) dimming Kim 6 'ied air inThe action of rhe @leci'ric arc, SGliiY'fliiflfI the resuiLiiig DHJ'OUSproducts m anhydrous mzids of nitrogen from ihe unz'ii- In :iiv ii'lei;iiuii n1 Cue 21im-te412gcribed 21p W 1 0i" Hi1 fig- 0 tim ziiimuiii',i'ereCi (iii- Z2341diSCh&1',iZ1;SUCh un:iii.ei'e 1 air. 60

my 1 iii lifi ilisciizwgze'ia 6. The pmeess of producing: COiX'iQGUHGSof "n 0; 'niiwgeii and oxygen, consisting: in remsviiigz iiie moisturefrom air by COOiiii lI aiiiijestiiig are the dried air to the action oftha eiecii'ic are, 70ii1WLii301lii moiin; he m'z-emeve by condensation-65 amountaf the iii'il'cfiiifi products, and sepai'ating suchsmnY-iaiiy cmicimiszad pi'niiuvrs. i021 the 7. The pIUlBGSS of producingcampoumifii of arcs on ii ifififi' ii and OI YQ-i",il., ceiisistiiig inexposing fOi'mQd. 0f iii-3 gases m the lbiiilOE'i ()f (in in- 7c- Iim'ia150W i '"i iruii mi in an viecwiu circuit, and

51' eieeti'enioiiw forces i-esirii .i he iz'ncess of pimiuc'ing (romgmumis 0f aousisting iii establish- 1 iii 5 .0

"cci riwaui iii the form of an me of mi 2 QUIZBi-i.

Sspcember 39,

7 mid Dimmict R035 Lovejwy, of New ip iiiczii-ion of Char c5 1 Z." uvrmT-nisvi: in Pmcesam of iiiainuffiicturmg Nitrogen Compounds @11 :marm): zi tipezii'ii in the printml h' icciili-siion requiring milliiimwz On pug: 4, line 013 0131i and insuiiemi after the word "are."line .27 same mi e: and that the in the Patent Q of October, 3).,

F. I. ALLEN,

(ommissio'n 01' of Paients.

It is hereby certified that in Letters Patent No. 709,867, grantedSeptember 30, 1902, upon the application of Charles S. Bradley andDimmitt Ross Lovejoy, of New York, N. Y., for an improvement inProcesses of Manufacturing Nitrogen Compounds from Atmospheric Nitrogen,an error appears in the printed specification requiring correction, asfollows: On page 4, line 30, the words of minimum volume should bestricken out and inserted after the word arc, line 27, same page; andthat the said. Letters Patent should be read withthis correction thereinthat the same may conform to the record of the case in the PatentOflice.

Signed and sealed this 21st day of October, A. 1)., 1902.

F. I. ALLEN,

Commissioner of Patents.

[SEAL]

